Autocatalytic polyols

Abstract

The present invention provides polymeric polyol compositions employing polyol compounds having multiple tertiary amine groups. Methods of making these compositions are also disclosed. Polyol formulations containing these polymeric polyol compositions and methods of making polyurethane gel and foam employing such polymeric polyol compositions are also provided.

1. A polymeric polyol composition comprising a contact product of:
 (a) a polymeric amine composition comprising amine compounds having the formula: 
 
       
         
           
           
               
               
           
         
         wherein: 
         each R A  is methyl 
         each R B  is a C 3  linear alkanediyl; 
         each X is R C —NH 2 ; 
         R C  is a C 3  linear alkanediyl; 
         n is an integer in a range from 0 to 10; and 
         the polymeric amine composition has a number-average molecular weight (Mn) from about 250 to about 1500; and 
         (b) at least one epoxide compound having the formula: 
       
       
         
           
           
               
               
           
         
         at least one glycidyl ether compound having the formula: 
       
       
         
           
           
               
               
           
         
         
           a combination thereof; 
         
         wherein:
 R Y  is hydrogen, phenyl, cyclohexyl, or a C 1 -C 18  linear or branched alkyl; 
 R Z  is hydrogen, phenyl, a C 1 -C 6  linear or branched alkyl-substituted phenyl, or a C 1 -C 18  linear or branched alkyl. 
 
       
     
     
       2. The composition of  claim 1 , wherein R Y  is hydrogen, methyl, or phenyl. 
     
     
       3. The composition of  claim 1 , wherein R Z  is methyl, ethyl, propyl, butyl, hexyl, 2-ethylhexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, phenyl, or butyl-substituted phenyl. 
     
     
       4. The composition of  claim 1 , wherein the polymeric amine composition has a number-average molecular weight (Mn) from about 300 to about 800. 
     
     
       5. The composition of  claim 1 , wherein the polymeric polyol composition has a weight-average molecular weight (Mw) from about 400 to about 20,000. 
     
     
       6. The composition of  claim 1 , wherein the polymeric polyol composition has a weight-average molecular weight (Mw) from about 1,000 to about 5,000. 
     
     
       7. The composition of  claim 1 , wherein the polymeric polyol composition has a hydroxyl number from about 5 to about 600 mg KOH/g. 
     
     
       8. The composition of  claim 1 , wherein the polymeric polyol composition has an amine value from about 10 to about 800 mg KOH/g. 
     
     
       9. The composition of  claim 1 , wherein the polymeric polyol composition has a hydroxyl equivalent weight (EW) from about 100 to about 10,000. 
     
     
       10. The composition of  claim 1 , wherein the polymeric amine composition and the at least one epoxide compound or at least one glycidyl ether compound, or a combination thereof, are reacted in the presence of a catalyst. 
     
     
       11. A polyol formulation comprising a contact product of:
 (i) polymeric polyol composition of  claim 1 ; and 
 (ii) at least one second polyol, wherein the at least one second polyol is at least one polyether polyol, at least one polyester polyol, or at least one polymer polyol, or any combination thereof. 
 
     
     
       12. The polyol formulation of  claim 11 , wherein a weight ratio of the polymeric polyol composition to the at least one second polyol is in a range from about 10:1 to about 1:1,000. 
     
     
       13. A method of making a polyurethane comprising contacting at least one polyisocyanate with the polyol formulation of  claim 11  in the presence of a catalytically effective amount of a catalyst composition under conditions sufficient to produce the polyurethane. 
     
     
       14. The method of  claim 13 , wherein the catalyst composition is present in an amount from about 0.01 to about 20 parts by weight per hundred weight parts of the polyol formulation (pphp). 
     
     
       15. The method of  claim 13 , wherein the contacting of the at least one polyisocyanate and the polyol formulation occurs in the presence of at least one blowing agent under conditions sufficient to produce a polyurethane foam. 
     
     
       16. The method of  claim 15 , wherein the at least one blowing agent is water, methylene chloride, acetone, a chlorofluorocarbon, a hydrofluorocarbon, a hydrochlorofluorocarbon, or a hydrocarbon, or any combination thereof. 
     
     
       17. The method of  claim 15 , wherein the polyurethane foam is substantially free of volatile amines and/or amine odors. 
     
     
       18. The method of  claim 15 , wherein the contacting of the at least one polyisocyanate and the polyol formulation occurs in the presence of at least one additive, wherein the at least one additive is at least one crosslinker, at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, or at least one pigment, or any combination thereof. 
     
     
       19. A composition comprising a contact product of:
 (i) at least one polyisocyanate; and 
 (ii) a polyol formulation comprising a polymeric polyol composition, wherein the polymeric polyol composition comprises a contact product of:
 (a) a polymeric amine composition comprising amine compounds having the formula: 
 
 
       
         
           
           
               
               
           
         
         wherein: 
         each R A  is methyl; 
         each R B  is a C 3  linear alkanediyl; 
         each X is a R C —NH 2 ; 
         R C  is a C 3  linear alkanediyl; 
         n is an integer in a range from 0 to 10; and 
         the polymeric amine composition has a number-average molecular weight (Mn) from about 250 to about 1500; and
 (b) at least one epoxide compound having the formula: 
 
       
       
         
           
           
               
               
           
         
         at least one glycidyl ether compound having the formula: 
       
       
         
           
           
               
               
           
         
         
           a combination thereof; 
         
         wherein:
 R Y  is hydrogen, phenyl, cyclohexyl, or a C 1 -C 18  linear or branched alkyl; 
 R Z  is hydrogen, phenyl, a C 1 -C 6  linear or branched alkyl-substituted phenyl, or a C 1 -C 18  linear or branched alkyl. 
 
       
     
     
       20. The composition of  claim 19 , wherein the at least one polyisocyanate comprises hexamethylene diisocyanate, isophorone diisocyanate, diphenyl methane diisocyanate, toluene diisocyanate, prepolymers of isocyanates or a combination thereof. 
     
     
       21. The composition of  claim 19 , wherein the polyol formulation further comprises at least one second polyol, and wherein the at least one second polyol is at least one polyether polyol, at least one polyester polyol, or at least one polymer polyol, or any combination thereof. 
     
     
       22. The composition of  claim 19 , further comprising at least one urethane catalyst, wherein the least one urethane catalyst is at least one gelling urethane catalyst or at least one blowing urethane catalyst, or a combination thereof. 
     
     
       23. The composition of  claim 19 , further comprising at least one additive, wherein the at least one additive is at least one crosslinker, at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, or at least one pigment, or any combination thereof. 
     
     
       24. A method for preparing a polyurethane foam comprising:
 (A) forming a premix comprising: 
 (i) a polyol formulation comprising an autocatalytic polymeric polyol composition; 
 (ii) about 0.5 to about 50 pphp blowing agent; 
 (iii) zero to about 20 pphp water; 
 (iv) about 0.05 to about 10 pphp crosslinker; 
 (v) about 0.5 to about 10 pphp silicon surfactant; 
 (vi) zero to about 50 pphp flame retardant; 
 (vii) zero to about 20 pphp of a gelling catalyst or a blowing catalyst, or a combination thereof; 
 wherein the polymeric polyol composition comprises a contact product of: 
 (a) a polymeric amine composition comprising amine compounds having the formula: 
 
       
         
           
           
               
               
           
         
         wherein: 
         each R A  is methyl; 
         each R B  is a C 3  linear alkanediyl; 
         each X is a R C —NH 2 ; 
         R C  is a C 3  linear alkanediyl; 
         n is an integer in a range from 0 to 10; and 
         the polymeric amine composition has a number-average molecular weight (Mn) from about 250 to about 1500; and 
         (b) at least one epoxide compound having the formula: 
       
       
         
           
           
               
               
           
         
         at least one glycidyl ether compound having the formula: 
       
       
         
           
           
               
               
           
         
         
           a combination thereof; 
         
         wherein:
 R Y  is hydrogen, phenyl, cyclohexyl, or a C 1 -C 18  linear or branched alkyl; 
 
         R Z  is hydrogen, phenyl, a C 1 -C 6  linear or branched alkyl-substituted phenyl, or a C 1 -C 18  linear or branched alkyl; and 
         (B) contacting the premix with at least one polyisocyanate at an Isocyanate Index from about 40 to about 800. 
       
     
     
       25. An article of manufacture comprising the polyurethane foam prepared by the method of  claim 24 . 
     
     
       26. The article of manufacture of  claim 25  wherein the foam has a density of about 20 to about 250 Kg/m 3 . 
     
     
       27. The article of manufacture of  claim 25  wherein the foam has thermal stability up to about 150 C. 
     
     
       28. The composition of  claim 1  further comprising at least one second polyol.